Lower alkoxyphenylazo - 1 - phenyl-3-carboxy-5-pyrazolone dyes containing substituted on the alkoxyphenyl group the sulfuric acid ester of a beta-hydroxyethyl sulfone group



United States Patent US. Cl. 260-163 12 Claims ABSTRACT OF THEDISCLOSURE Monoazo dyes represented by the formula,

wherein R stands for methyl or ethyl group, R stands for hydrogen atom,methyl or ethyl, and one of X stands for SO CH CH OSO H and another Xstands for hydrogen atom, methyl, methoxy or ethoxy, and the ring Ameans sulfophenyl or sulfophenyl substituted with methyl, chlorine ormethyl and chlorine. These new dyes are particularly suitable forprintor pad-dyeing of natural or regenerated cellulose fibers in abrilliant reddish yellow tint with good fastness to light and to wetprocessing.

This invention provides valuable novel yellow monoazo dyes representedby the general formula:

wherein R stands for a methyl or ethyl group, and R stands for ahydrogen atom, methyl or ethyl group, and one of X stands for a grouprepresented by and another X stands for a hydrogen atom, methyl, methoxyor ethoxy group and ring A is sulfophenyl or sulfophenyl substituted byalkyl, halo or alkylyl and halo acid group and may further contain alkylgroups and/or halogen atoms.

The invention also provides a process for the manufacture of theaforesaid novel monoazo dyes, which comprises contacting a diazotizedamine of the formula:

in which R stands for a methyl or ethyl group, and one of Y stands for agroup represented by SO CH CH OH and another Y stands for a hydrogenatom, methyl, methoxy or ethoxy group, in the form of its acid sulfuricacid ester with 1-pheny1-3-carboxy-5-pyrazolones and their ice methyl orethyl esters, in which the phenyl radical contains at least one sulfonicacid group and may further contain alkyl groups and/ or halogen atoms,or after contacting the aforesaid amine with the said 1-phenyl-3-carboxy-S-pyrazolone derivatives, esterifying the dyes derived withsulfuric acid at the hydroxy group of the fl-hydroxyethyl group.

The dyes of the present invention represented by the above generalformula are suitable for dyeing the fibre, especially for those madefrom natural or regenerated cellulose materials such as cotton, linen,viscose, and polyvinyl alcohol materials and yield clear reddish yellowdyeings.

The dyeing in accordance with the present invention is effected, as inthe ordinary fibre reactive dyes, in the presence of acid binding agentsby the methods such as im pregnation, printing and padding. It is alsopossible by fixing the dyes with the acid binding agents after theprinting or padding without any fixing agents.

The dyeings obtained in accordance with the present invention aredistinguished by a brilliant reddish yellow tint and good fastnesses tolight and wet processing, moreover, the dyes of the present inventionare especially distinguished by a good solubility in water and a goodstability of the alkaline paste for printing.

The following examples illustrate the invention, the parts being byweight, and are not intended to limit the invention.

EXAMPLE 1 27.8 parts of 2-methoxyaniline-5-B-hydroxyethyl-sulfone isadded into parts of sulfuric acid of strength at 20 C. to 30 C. Aftercomplete dissolution the mixture is stirred for 1 hour and thenintroduced into 300 parts of ice and water. The precipitated sulfuricacid ester is filtered. The obtained ester is introduced into 350 partsof me and water and diazotized with 16 parts of hydrochloric acid andaqueous 8.3 parts of sodium nitrite.

34.2 parts of 1-(4'-sulfophenyl)-3-carboxy-5-pyrazolone are dissolvedneutral in 300 parts of water and 15 parts of sodium carbonate, and intothis solution the fores'aid diazo mixture is introduced dropwise, duringthen about 10 parts of sodium bicarbonate is added to maintain thereaction within pH 6-7. After the reaction is over, parts of sodiumchloride are added thereto and the precipitated dyes are filtered anddried at 70 C.

Thus 5 6 parts of the dyes represented by the following formula areobtained.

OCH;

, 0 H Q OaSOHzCHzCOgS J O 0 H The dye obtained is an orange yellowpowder which easily dissolves in water and gives reddish ellow dyeingsof good fastnesses to wet processing and light and of a high brilliancyon natural or regenerated cellulose fibres with the aid of acid bindingagents through the usual dyeing method of the fibre reactive dyes.

EXAMPLE 2 of sodium carbonate and into this solution the aforesaid diazomixture is introduced dropwise. After the coupling reaction is over, 20parts of sodium chloride are added and the precipitated dyes arefiltered, dried and pulverized.

The dye obtained is added into 70 parts of sulfuric acid of 98% strengthat 20 C. After complete dissolution, the mixture is stirred for 2 hoursand then introduced into 200 parts of ice and water. 20 parts ofpotassium chloride is added and the precipitated dye is filtered. Thecake obtained is dissolved in 150 parts of ice and water and the mixtureis adjusted to pH 6-7 with aqueous potassium carbonate. The mixture issalted out with parts of potassium chloride and the precipitated dyesare filtered and dried at 70 C.

Thus 18 parts of the dyes same as in Example 1 are obtained.

EXAMPLE 3 36.8 parts ofZ-methoxy-S-methylaniline-4-fi-hydroxyethylsulfone is added into 70parts of sulfuric acid of 98% strength at 1530 C. After completedissolution the mixture is stirred for 2 hours and then introduced into300 parts of ice and water. The precipitated sulfuric acid ester isfiltered. The obtained ester is introduced into 350 parts of ice andwater and diazotized with 16 parts of hydrochloric acid and aqueous 8.3parts of sodium nitrite.

34.2 parts of l-(4'-sulfophenyl)-3-carboxy-5-pyrazolone is dissolvedneutral in 300 parts of water and 10.2 parts of sodium bicarbonate, andinto this solution the foresaid diazo mixture is introduced dropwise,during then about parts of sodium carbonate is added to maintain thereaction within pH 6-7. After the reaction is over, 160 parts ofpotassium chloride is added and the precipitated dyes are filtered anddried at 70 C.

Thus 65 parts of the dyes represented by the following formula areobtained.

The dye obtained is an orange yellow powder which easily dissolves inwater and gives reddish yellow dyeings of good fastnesses to wetprocessing and light and of high brilliancy on natural or regeneratedcellulose fibres with the aid of acid binding agents through the usualdyeing method of the fibre reactive dyes.

EXAMPLE 4 10.8 parts of2-methoxy-S-methylaniline-4-fi-hydroxyethylsulfone is added into 100parts of ice and water containing 5.5 parts of hydrochloric acid, andare diazotized with 2.8 parts of sodium nitrite.

11.4 parts of 1-(4-sulfophenyl)-3-carboxy-5-pyrazolone are added into100 parts of water and 8 parts of sodium carbonate, and into thissolution the foresaid diazo mixture is introduced dropwise. After thecoupling reaction is over, parts of potassium chloride are added and theprecipitated dye is filtered, dried and pulverized.

The dye obtained is added into 100 parts of sulfuric acid of 100%strength at 20 C. After complete dissolution, the mixture is stirred for2 hours and then introduced into 200 parts of ice and Water, andneutralized to pH 6-7 with potassium carbonate. 15 parts of potassiumchloride is added thereto and the precipitated dye is filtered and driedat 70 C.

Thus 19 parts of the dye same to Example 3 is obtained.

EXAMPLE 5 In a similar way as in Examples 1 to 4, each dyes of thestructures shown in the column I in the following table are obtained andgive dyeings of good fastnesses to light and wet processing and ofdistinguished brilliancy in tint indicated in the column II.

(1) (Structure) (11) (Tint) Reddish Yellow 0 o m O l p N soarnoasomomools v =N/ Reddish Yellow 0 CH3 noasomorrzools =N ReddislrYellow 0 on.

i on

l nossomomools "N/ 3 0 o H S 0 311 Yellow 0 on:

I OH or L N S 03H noasonzomools =N c 0 OH CH3 Yellow 0 on,

I I on or N=N-=K I N- S 0 3H nolsomomools =N c o o our 91 Yellow 0cm 0 HCH3 N=N=K N sotn nossonlomoors =N oooolm Yellow OCH:

0 H or -N=N- N noasomonlooa =N I o 0 OH 8 03H Reddish Yellow OCH:

0 H S 0 all N=N K I N HOJSOHgOHzCOaS =N oooozni so 311 Reddish Yellow00H;

0 rr moo-O41:

norsorrzonloozs =N Reddish Yellow CzHs COOH Reddish Yellow 0 C2115 0 HN=N- -L l N S0311 Hoasonzcnlcols =N Reddish Yellow 0 CH3 OH nolsomcmo02sC -N=N-= I N S 03H 1130 N Reddish Yellow 0 OH;

OH HO3SOHzCH2CO2S N=N= C O O H S 0311 Reddish Yellow 0 CH3 1 0H CH3 HO3SOH2CHzCO2S-ON=N"= I NC SO;H

Reddish Yellow 0 OH:

I 0 H 01 HO3SOHQCH2COZSON= I N S 0311 H c 0 0 0 02115 01 Reddish YellowOH CH3 HOaSOHaCHzCOzS-ON=N% O Reddish Yellow OCH;

I OH H0 SOHzOH CO SON=N-= N- -S 03H OOOH Orange Yellow OOH:

OH HOaSOHgCHzCOzS -N=N= Orange Yellow OCH;

OH HOgSOHgCHzCOzS- N= Orange Yellow 002115 OH HOaSOHflCHzCOzS- may-AJOOH What We claim is:

1. A monoazo dye represented by the following formula:

l OH

N A X =N COOR2 GOOH HOaSOHzCHzC 02 S 3. A monoazo dye represented by thefollowing formula:

OCHa

COOH

4. A monoazo dye represented by the following formula:

OCHa

COOH

HOaSHOzOHzCOzS- 5. A monoazo dye represented by the following forrnula:

6. A monoazo dye represented by the following forrnula:

7. A monoazo ,dye represented by the following formula:

8. A monoazo dye represented by the following formula:

I OH

N=N --i N 50311 HOsSOl-IzCI-IzCOzS =N coon 9. A monoazo dye representedby the following formula:

OH nmsomomcmsOnan-A l NOSO3H H5025 10. A monoazo dye represented by thefollowing formula:

Ho3s0H20H200 s-O N=N% I N- -son1 1130 :N/

11. A monoazo dye represented by the following f0rmula:

I N S 0 3H HO SQHZCH COgS =N 12. A monoazo dye represented by thefollowing formula:

OCH;

I N- SO3H HOaSOHzCHaCOzS =N References Cited UNITED STATES PATENTS2,195,390 3/1940 Ellis et a1. 260163 2,670,265 2/ 1954 Heyna et a1.260-163 XR 2,728,762 12/1955 Heyna et al. 260--163 2,842,537 7/1958Strobel et a]. 260-163 3,170,912 2/1965 Freyermuth et al. 260 1633,234,207 2/1966 Berner et al. 260-163 XR 3,379,715 4/1968 Chiddix etal. 260163 3,385,843 5/1968 Remy et a1. 260163 FLOYD D. HIGEL, PrimaryExaminer US. Cl. X.R.

